WO2015058826A1 - Materialien für elektronische vorrichtungen - Google Patents

Materialien für elektronische vorrichtungen Download PDF

Info

Publication number
WO2015058826A1
WO2015058826A1 PCT/EP2014/002586 EP2014002586W WO2015058826A1 WO 2015058826 A1 WO2015058826 A1 WO 2015058826A1 EP 2014002586 W EP2014002586 W EP 2014002586W WO 2015058826 A1 WO2015058826 A1 WO 2015058826A1
Authority
WO
WIPO (PCT)
Prior art keywords
radicals
atoms
substituted
aromatic ring
ring system
Prior art date
Application number
PCT/EP2014/002586
Other languages
German (de)
English (en)
French (fr)
Inventor
Arne Buesing
Irina Martynova
Frank Voges
Jonas Valentin Kroeber
Original Assignee
Merck Patent Gmbh
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Merck Patent Gmbh filed Critical Merck Patent Gmbh
Priority to EP14772289.6A priority Critical patent/EP3060623B1/de
Priority to CN201480057646.1A priority patent/CN105722944A/zh
Priority to US15/030,565 priority patent/US9859502B2/en
Priority to KR1020167013361A priority patent/KR102279289B1/ko
Priority to JP2016525945A priority patent/JP6469673B2/ja
Priority to KR1020217021857A priority patent/KR20210091355A/ko
Publication of WO2015058826A1 publication Critical patent/WO2015058826A1/de

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
    • C07C209/74—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton by halogenation, hydrohalogenation, dehalogenation, or dehydrohalogenation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/54—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to two or three six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/57—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton
    • C07C211/61—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton with at least one of the condensed ring systems formed by three or more rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/91—Dibenzofurans; Hydrogenated dibenzofurans
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/622—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing four rings, e.g. pyrene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/02—Ortho- or ortho- and peri-condensed systems
    • C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
    • C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
    • C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
    • C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
    • C07C2603/18—Fluorenes; Hydrogenated fluorenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/02—Ortho- or ortho- and peri-condensed systems
    • C07C2603/52—Ortho- or ortho- and peri-condensed systems containing five condensed rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/56—Ring systems containing bridged rings
    • C07C2603/90—Ring systems containing bridged rings containing more than four rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/93—Spiro compounds
    • C07C2603/95—Spiro compounds containing "not free" spiro atoms
    • C07C2603/96—Spiro compounds containing "not free" spiro atoms containing at least one ring with less than six members
    • C07C2603/97—Spiro compounds containing "not free" spiro atoms containing at least one ring with less than six members containing five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1007—Non-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1011—Condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1014—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/18—Metal complexes
    • C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/15—Hole transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/15—Hole transporting layers
    • H10K50/155—Hole transporting layers comprising dopants
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/17—Carrier injection layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/18—Carrier blocking layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/623—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing five rings, e.g. pentacene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/624—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing six or more rings
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the present invention relates to materials for use in electronic devices, especially in organic ones
  • Electroluminescent devices are Electroluminescent devices.
  • the development of functional compounds for use in electronic devices is currently the subject of intense research.
  • the aim in particular is the development of compounds with which improved properties of the electronic devices can be achieved in one or more relevant points, such as power efficiency, lifetime or color coordinates of the emitted light.
  • OICs organic integrated circuits
  • OFETs organic field effect transistors
  • OFTs Thin-film transistors
  • OLETs organic light-emitting transistors
  • OSCs organic solar cells
  • OFQDs organic field quench devices
  • OLEDs organic light-emitting electrochemical cells
  • O-lasers organic laser diodes
  • OLEDs organic electroluminescent devices
  • Improvements are needed, especially with a view to widespread commercial use, for example in display devices or as light sources. Of particular importance are in this
  • the efficiency and the operating voltage of the OLEDs as well as the realized color values are related to the lifetime, the efficiency and the operating voltage of the OLEDs as well as the realized color values. Especially with blue-emitting OLEDs there is potential for improvement with regard to the lifetime of the devices.
  • the compounds for use as functional materials in electronic devices have a high thermal stability and a high thermal stability
  • the document CN 102030701 A describes compounds with indeno [1, 2,3-jk] fluorene skeleton.
  • the document US 2006/0094859 A1 describes polymers with multiply bridged biphenyl units.
  • Hole transport / electron blocking material or exciton blocking material and / or as electron transport or hole blocking material are also possible.
  • the present invention therefore provides a compound according to formula (1),
  • Z is the same or different CR 1 or N at each occurrence
  • Ar 1 is the same or different at each occurrence and is an aromatic or heteroaromatic ring system having from 5 to 60 aromatic
  • Ring atoms which may be substituted by one or more R 3 radicals; two Ar 1 radicals which bind to the same N atom or P atom may also be bridged together by a single bond or a bridge selected from N (R 4 ), C (R 4 ) 2 , O or S;
  • Ring system having 6 to 60 aromatic ring atoms, each of which may be substituted by one or more radicals R 4 , or a heteroaromatic ring system having 5 to 60 aromatic
  • Ring atoms which may 4 be substituted with one or more radicals (n) R, where two or more radicals R 4 may be bonded together and may form a ring; is identical or different at each occurrence, H, D, F, CN or an aliphatic radical having 1 to 20 C atoms, or an aromatic ring system having 6 to 60 aromatic ring atoms or a heteroaromatic ring system having 5 to 60 aromatic radicals (n) R, where two or more radicals R 4 may be bonded together and may form a ring; is identical or different at each occurrence, H, D, F, CN or an aliphatic radical having 1 to 20 C atoms, or an aromatic ring system having 6 to 60 aromatic ring atoms or a heteroaromatic ring system having 5 to 60 aromatic
  • Ring atoms wherein in the aliphatic radical, the aromatic ring system or the heteroaromatic ring system one or more H atoms by D, F, Cl, Br, I, CN or an alkyl group with 1 to 5 carbon atoms may be replaced, wherein two or more radicals R 4 may be linked together and form a ring; wherein R 2 and / or at least one R 1 of formula (1) comprises at least one aromatic or heteroaromatic ring system, and when at least one R 1 at least one aromatic or
  • aromatic ring atoms in all R 1 and R 2 is at least 12; and when R 1 does not comprise an aromatic or heteroaromatic ring system, R 2 comprises at least 24 aromatic ring atoms, and no further indeno [1,2,3-jk] fluorene skeleton linked via the 12-position.
  • An aryl group in the sense of this invention contains 6 to 60 aromatic ring atoms; a heteroaryl group in the context of this invention contains in principle 5 to 60 aromatic ring atoms, of which at least one represents a heteroatom.
  • the heteroatoms are preferably selected from
  • N O and / or S. This is the basic definition. If other preferences are given in the description of the present invention, such as the number of aromatic ring atoms or the heteroatoms contained therein, these apply.
  • an aryl group or heteroaryl group is either a simple aromatic cycle, ie benzene, or a simpler one
  • heteroaromatic cycle for example pyridine, pyrimidine, thiophene, etc., or a condensed (fused) aromatic or
  • heteroaromatic polycycle for example naphthalene, anthracene, phenanthrene, quinoline, isoquinoline, or carbazole.
  • Polycycle consists in the context of the present application of two or more condensed simple aromatic or heteroaromatic cycles.
  • aromatics linked to one another by single bond for example biphenyl or bipyridine, are not designated as aryl or heteroaryl group but as aromatic ring system.
  • benzene in particular groups derived from benzene, naphthalene, anthracene, phenanthrene, pyrene, dihydropyrene, chrysene, perylene, fluoranthene, benzanthracene, benzphenanthrene, tetracene, pentacene, benzopyrene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, Dibenzothiophene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine,
  • Phenanthndine benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, naphthimidazole, phenanthrimidazole, pyrimididazole, pyrazine imidazole, quinoxaline imidazole, oxazole, Benzoxazole, naphthoxazole, anthroxazole, phenanthroxazole, isoxazole, 1, 2-thiazole, 1, 3-thiazole, benzothiazole,
  • An aromatic ring system in the sense of this invention contains 6 to 60 aromatic ring atoms in the ring system.
  • Ring system in the context of this invention contains 5 to 60 aromatic radicals
  • Ring atoms at least one of which represents a heteroatom.
  • the heteroatoms are preferably selected from N, O and / or S.
  • Unter ein aromatic or heteroaromatic ring system in the context of this invention is to be understood as a system which does not necessarily contain only aryl or heteroaryl groups, but in which also several aryl or heteroaryl groups by a non-aromatic moiety
  • an sp -hybridized C, Si, N or O atom, an sp -hybridized C or N atom, or a sp-hybridized C atom can be joined.
  • systems such as 9,9'-spirobifluorene, 9,9'-diaryl fluorene, triarylamine, diaryl ether, stilbene, etc. as aromatic
  • Ring systems are understood within the meaning of this invention, and also systems in which two or more aryl groups are connected for example by a linear or cyclic alkyl, alkenyl or alkynyl group or by a silyl group. Furthermore, systems, in
  • Single bonds are linked together, understood as aromatic or heteroaromatic ring systems in the context of this invention, such as systems such as biphenyl, terphenyl or diphenyltriazine.
  • aromatic or heteroaromatic ring system having 5-60 aromatic ring atoms, which may be substituted in each case by radicals as defined above and which may be linked via any desired positions on the aromatic or heteroaromatic compounds, is especially preferred
  • alkoxy or thioalkyl group having 1 to 40 carbon atoms methoxy, trifluoromethoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, n-pentoxy, s Pentoxy, 2-methylbutoxy, n-hexoxy, cyclohexyloxy, n-heptoxy, cycloheptyloxy, n-octyloxy,
  • a maximum of one group Z per cycle is N and the other groups Z are the same or different at each occurrence for CR 1 . In a particularly preferred embodiment of the invention, all groups Z are the same or different at each occurrence for CR 1 .
  • At least one R is at least one aromatic or
  • the total number of aromatic ring atoms in all R 1 and R 2 is at least 12, preferably at least 18, more preferably at least 24.
  • R 1 does not comprise an aromatic or heteroaromatic ring system
  • R 2 comprises at least 24 aromatic ring atoms, and no further lndeno [1, 2,3-jk] fluorene scaffold.
  • the 12-position represents the most acidic position of the framework in lndeno [1, 2,3-jk] fluorene frameworks. Therefore, these bonds are particularly unstable. If there are other indeno [1,2,3-jk] fluorene frameworks in the compound, it not only becomes very large, but also potentially more unstable.
  • R 1 and / or R 2 do not comprise fused aromatic or heteroaromatic ring systems having more than 14 aromatic
  • all R 1 and R 2 together comprise a total number of aromatic ring atoms of not more than 84, preferably not more than 60.
  • Preferred embodiment of the compound of the formula (1) is therefore a compound of the following formula (2):
  • R 1 in the abovementioned formulas is the same or different at each occurrence as H, D, F, CN, NO 2 , N (Ar 1 > 2, N (R 3 > 2, a straight-chain alkyl or alkoxy group having 1 to 10 C atoms or a branched or cyclic alkyl or alkoxy group having 3 to 10 C atoms or an alkenyl or alkynyl group having 2 to 10 C atoms, wherein the alkyl, alkoxy, alkenyl or
  • Alkynyl may be substituted by one or more radicals R 3 and wherein one or more non-adjacent CH 2 groups may be replaced by Si (R 3 > 2, -S- and -O- and wherein one or more H atoms by D or F can be replaced, or an aromatic
  • Ring system having 6 to 30 aromatic ring atoms, each of which may be substituted by one or more radicals R 3 , or a
  • R 2 in the abovementioned formulas is, identically or differently, H, D, F, CNN (Ar) 2 L N (R 3 ) 2 , a straight-chain alkyl or alkoxy group having 1 to 10 C atoms or a branched or cyclic alkyl or
  • Alkynyl group may be substituted by one or more radicals R 3 and wherein one or more non-adjacent CH 2 groups may be replaced by Si (R 3 ) 2 , -S- and -O- and wherein one or more H atoms by D or F can be replaced, or an aromatic one
  • Ring system having 6 to 30 aromatic ring atoms, each of which may be substituted by one or more radicals R 3 , or a
  • heteroaromatic ring system having 5 to 30 aromatic ring atoms, each of which may be substituted by one or more radicals R 3 .
  • R 2 in the abovementioned formulas is an aromatic ring system having 6 to 30 aromatic ring atoms which may be substituted by one or more radicals R 3 .
  • Ring system having 5 to 18 aromatic ring atoms, which may be substituted in each case 4 with one or more radicals (n) R, where two or more radicals R 4 may be bonded together and may form a ring.
  • R 1 is the same or different H, D, F, CN, NO 2 , N at at least one of the positions 5 or 10 of the indeno [1,2,3-jk] fluorene skeleton.
  • Ar 1 ) 2 , N (R 3 ) 2, C ( 0)
  • heteroaromatic ring system having 5 to 60 aromatic ring atoms, each of which may be substituted by one or more radicals R 3 , wherein two or more radicals R 1 may be linked together and form a ring.
  • R contains the
  • the alkyl groups preferably have not more than 4 carbon atoms.
  • At least one R 1 is not H, preferably at least one R 1 comprises an aromatic or heteroaromatic ring system.
  • Particularly preferred aromatic ring systems for R 1 or R 2 are selected from the group phenyl, ortho-, meta- or para-biphenyl, ortho-, meta- or para-terphenyl, ortho, meta, para or branched quaterphenyl , Fluorene, spirobifluorene, which may each be substituted by one or more radicals R 3 .
  • aromatic ring systems for R 1 or R 2 are in particular selected from the structures of the following formulas:
  • R 3 is preferably an aliphatic radical having 1 to 20 C atoms, or an aromatic ring system having 6 to 24 aromatic ring atoms or a
  • heteroaromatic ring system having 5 to 24 aromatic ring atoms, preferably an aliphatic radical having 1 to 10 carbon atoms or an aromatic ring system having 6 to 18 aromatic ring atoms.
  • heteroaromatic ring systems R 1 or R 2 contain, as heteroaryl group, triazine, pyrimidine, pyrazine, pyridazine, pyridine, benzothiophene, benzofuran, indole, carbazole, azacarbazole,
  • heteroaromatic groups may be substituted at all free positions with radicals R 3 and the heteroaromatic groups at any position with the indeno [1, 2,3-jk] fluorene- May also be substituted for NR 3 and wherein R 3 is as defined for formula (1) and the bond to the indeno [1,2,3-jk] fluorene skeleton also via a divalent aromatic or heteroaromatic ring system, preferably a divalent ring system according to one of the formulas (Ar3-1) to (Ar3-12), particularly preferably one of the formulas (Ar3-1) to (Ar3-4).
  • R 3 is an aliphatic radical having 1 to 20 C atoms, or an aromatic ring system having 6 to 24 aromatic ring atoms or a
  • heteroaromatic ring system having 5 to 24 aromatic ring atoms, preferably an aliphatic radical having 1 to 10 carbon atoms or a
  • aromatic ring system with 6 to 18 aromatic ring atoms.
  • R 1 or R 2 is a group N (Ar 1 ) 2, then this group is preferably selected from the structures of the following formulas (3) or (4),
  • R 1 , or R 2 is an aromatic or heteroaromatic ring system, which is a triarylamine or a
  • Triheteroarylamine is, then this group is preferably selected from the structures of the following formula (5): Ar 2
  • Ar 2 is the same or different and at each occurrence an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which may be substituted by one of the plurality of radicals R 3 ; the sum of the aromatic ring atoms of all groups Ar 2 and Ar 3 together is not greater than 60;
  • Ar 3 is at each occurrence an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which may be substituted with one of the plurality of R 3 ;
  • E is selected from the group consisting of a single bond, C (R 3 ) 2 , NR 3 , O or S.
  • Preferred ring systems for the formulas Ar 1 in formula (3) or Ar 2 in formula (5) are structures of the formulas (H-1) to (H-15), which may be substituted at all free positions with radicals R 3 and the heteroaromatic groups may be attached at any free position to the N atom of the formula, and structures of formulas (A-1) to (A-25) wherein the structures may be substituted with one or more R 3 and R 3 the dashed bond represents the bond to the N atom of the formula, and R 3 is defined as indicated above.
  • both Ar 2 in formula (5) are selected from the structures (A-2) to (A-25) or (H-7) to (H-9).
  • Ar 3 is selected from divalent groups of the following
  • Ar 3 is particularly preferably one of the structures (Ar 3-1 ) to (Ar3-4).
  • the compound comprises exactly 1, 2, 3, 4 or 5, preferably 1, 2 or 3, more preferably 1 or 2, radicals R 1 and / or R 2 selected from the formulas (3), (4) and (5), preferably from the formulas (3) and (5).
  • the compound contains exactly one radical R or R 2 selected from the formulas (3), (4) and (5).
  • Preferred embodiments of the compound of formula (1) are the compounds of formulas (1-3a) to (1-3g) and formulas (1-5a) to (1-5g):
  • Formula (1-5f) Formula (1-5g) wherein R 1 , R 2 , Ar 1 , Ar 2 and Ar 3 are as defined above.
  • Nitrogen atom preferably heteroatom, arranged in the para position on a 6-ring aryl system directly on the lndeno [1, 2,3-jk] fluorene skeleton. This also applies to fused aromatic ring systems containing carbazole structures which are bonded at the 3-position to the indeno [1,2,3-jk] fluorene skeleton. Surprisingly, it has been found that such compounds are significantly more unstable than compounds which have the nitrogen atom in the ortho or meta position.
  • R 2 is a heteroaromatic ring system
  • R 2 comprises as a heteroaromatic ring system a triarylamine or triheteroarylamine group or a carbazole structure which is bonded directly to the indeno [1,2,3-jk] fluorene skeleton
  • the nitrogen atom is present in meta or ortho Position with respect to which the indeno [1,2,3-jk] fluorene skeleton is arranged.
  • Ar 3 in formula (I-5a) is selected from the structures (Ar 3-2) to (Ar 3 -11), the bond to the indeno [1, 2,3-jk] fluorene is preferred.
  • Ar 3 is particularly preferably selected from the structures (Ar 3-2 ) and (Ar 3-3).
  • a preferred embodiment of the compound of formula (1-5a) is a compound of the formulas
  • Formula (1-5a-1) Formula (1-5a-2) wherein R 1 and Ar 2 are as defined above and the compound may be substituted at the free positions with one or more R 3 , but is preferably unsubstituted.
  • R 1 and R 2 are present in the formulas (1-3a) to (1-3g), (1-5a) to (1-5g), and
  • R 1 and R 2 are present in the formulas (1-3a) to (1-3g) and (1-5a) to (1-5g) and the formulas (1-5a 1) and (1-5a-2), no or exactly one further group selected from the formulas (3), (4) or (5) and at least one further R and / or R 2 if present an aromatic or heteroaromatic Ring system, particularly preferably an aromatic or heteroaromatic ring system of the formulas (A-1) to (A-25) or (H-1) to (H-14), very particularly preferably an aromatic ring system, in particular according to the formulas (A-1 ) to (A-25).
  • the more than one R 1 do not form with one another aromatic or heteroaromatic ring systems fused to the indeno [1,2,3-jk] fluorene skeleton.
  • aromatic or heteroaromatic ring system with 5 to 60
  • aromatic ring atoms which may be substituted by one or more R 3 radicals. Particularly preferred in this case
  • At least one R 1 and / or R 2 is selected from the formulas (3), (4) and (5) and their abovementioned embodiments.
  • At least one R 1 and / or R 2 is an aromatic or heteroaromatic ring system which contains at least one aryl group having at least three condensed six-membered rings, preferably anthracene.
  • at least one R 1 and / or R 2 is preferably an aromatic or heteroaromatic ring system containing at least one aryl group or an aromatic ring system having at least two condensed six-membered rings which is preferably bound directly or via a phenyl group to the indeno [1, 2,3-jk] fluorene skeleton.
  • the condensed aryl group is preferably selected from anthracene, pyrene, phenanthrene, chrysene, Monobenzoindenofluoren or
  • Electron transport material can be used, is preferred
  • heteroaromatic ring system having 5 to 40 aromatic ring atoms, preferably having 5 to 25 aromatic ring atoms, which may be substituted by one or more radicals R 3 .
  • heteroaromatic ring system in the context of the present invention is a heteroaromatic ring system which at least one
  • heteroaryl group which is either a 6-ring heteroaryl group having at least one nitrogen atom or a 5-ring heteroaryl group having at least two heteroatoms.
  • heteroaromatic ring systems R and / or R 2 contain as heteroaryl at least one group selected from triazine, pyrimidine, pyrazine, pyridazine, pyridine, imidazole, pyrazole, oxazole, oxadiazole, triazole, thiazole, thiadiazole, benzimidazole, quinoline, isoquinoline and quinoxaline ,
  • the heteroaromatic ring systems are in particular selected from the structures of the formulas (H-1), (H-2), (H-3), (H-14), where R 3 has the meanings mentioned herein and the structures on a free Position over one Single bond or via a phenyl group to the indeno [1, 2,3-jk] fluorene skeleton are bonded.
  • At least one R 1 and / or R 2 is preferably N (Ar 1 ) 2 , one
  • Triarylaminoolitic ring system having 5 to 40 aromatic ring atoms, in particular 5 to 25 aromatic ring atoms, which may be substituted by one or more radicals R 3 , in particular a radical according to the above formulas (3), (4) or (5).
  • R 3 a radical according to the above formulas (3), (4) or (5).
  • heteroaromatic ring system according to the invention is a
  • heteroaromatic ring system which has at least one
  • electron-rich heteroaryl group which is a 5-ring heteroaryl group having exactly one heteroatom to which one or more aryl groups may be fused.
  • Particularly preferred electron-rich heteroaromatic ring systems R 1 and / or R 2 contain as heteroaryl pyrrole, furan, thiophene, benzothiophene, benzofuran, indole, carbazole, dibenzothiophene,
  • the electron-rich heteroaromatic ring systems are in particular selected from the structures of the abovementioned formulas (H-4) to (H-13).
  • Such compounds can be prepared, for example, by reaction of
  • X shark or other reactive leaving group
  • the compound obtained is introduced with the desired R 2 instead of the group Y.
  • R 2 comprises an aromatic ring system, this is preferably done via a Friedel-Crafts reaction.
  • W organic radical (if present), in particular N (Ar) 2
  • the starting compound is synthesized by a Grignard reaction to a CN group: Scheme 4a
  • the benzonitrile compound is the precursor compound for the later R 2.
  • Several radicals W can also form rings, as can fused (fused) rings, or together form an aromatic or heteroaromatic ring system, for example carbazoles.
  • W is preferably an R2N group, wherein R is preferably identical or different and is an aryl or heteroaryl group.
  • the radical W is an alkyl or arylamine. This can be introduced via a Buchwald coupling:
  • R H or organic radical, preferably aryl or heteroaryl group
  • X Hai or other reactive leaving group
  • the alkyl or arylamine group is ortho or meta to the nitrile group:
  • W organic radical (if present), in particular N (Ar) 2
  • a further subject of the present invention thus represents a process for the preparation of compounds according to formula (1), or (2), which is characterized in that starting from a0
  • Fluorenone derivative addition to the keto group and a preferably transition metal-catalyzed coupling reaction to ring closure to lndeno [1, 2,3-jk] fluorene scaffold performed. Another object of the present invention thus provides
  • Suitable reactive leaving groups are, for example, bromine, iodine, chlorine, boronic acids, boronic esters, amines, alkenyl or alkynyl groups with terminal CC double bond or CC triple bond, oxiranes, oxetanes, groups which have a cycloaddition, for example a 1, 3-dipolar cycloaddition to go down as
  • dienes or azides for example, dienes or azides, carboxylic acid derivatives, alcohols and silanes.
  • Another object of the invention are therefore oligomers, polymers or dendrimers containing one or more compounds of the formula (1), or (2), wherein the bond (s) to the polymer, oligomer or
  • Dendrimer can be located at any, in formula (1), or (2) substituted with R 1 and / or R 2 substituted positions. Depending on the linkage of the compound according to the invention, the compound is part of a side chain of the oligomer or polymer or constituent of the main chain.
  • An oligomer in the context of this invention is understood as meaning a compound which is composed of at least three monomer units.
  • a polymer in the context of the invention is understood as meaning a compound which is composed of at least ten monomer units.
  • the polymers, oligomers or dendrimers of the invention may be conjugated, partially conjugated or non-conjugated.
  • the oligomers or polymers of the invention may be linear, branched or dendritic.
  • the units of the formula (1) or (2) can be linked directly to one another or they can be linked via a divalent group, for example via a substituted or unsubstituted alkylene group, via a heteroatom or via a bivalent aromatic or heteroaromatic group be linked together.
  • branched and dendritic structures for example, 3, 5 or more units of formula (1), or (2) via a trivalent or higher valent group, for example via a trivalent or higher valent aromatic or heteroaromatic group, to a branched or dendritic oligomer or Being polymer linked.
  • the bonds to the oligomer, polymer or dendrimer are not located at both positions 5 and 10.
  • Suitable and preferred comonomers are selected from fluorenes (eg according to EP 842208 or WO 2000/22026), spirobifluorenes (eg according to EP 707020, EP 894107 or US Pat
  • WO 2006/061181 paraphenylenes (for example according to WO 1992/18552), carbazoles (for example according to WO 2004/070772 or WO 2004/1 13468), thiophenes (for example according to EP 1028136), dihydrophenanthrenes (eg according to WO 2005/014689 or WO 2007/006383), cis- and
  • ketones eg according to WO2005 / 040302
  • phenanthrenes eg according to WO 2005/104264 or WO 2007/017066
  • the polymers, oligomers and dendrimers usually contain further units, for example
  • fluorescent or phosphorescent units such as. Vinyltriarylamines (for example according to WO 2007/068325) or phosphorescent metal complexes (for example according to WO 2006/003000), and / or charge transport units, especially those based on triarylamines.
  • the polymers, oligomers and dendrimers according to the invention have advantageous properties, in particular high lifetimes, high efficiencies and good color coordinates.
  • the polymers and oligomers according to the invention are generally prepared by polymerization of one or more types of monomer, of which at least one monomer in the polymer to
  • the present invention thus also provides a process for the preparation of the polymers, oligomers and
  • Dendrimers which are characterized by being Polymerization according to SUZUKI, polymerization according to YAMAMOTO, polymerization according to SILENCE or polymerization according to HARTWIGBUCHWALD.
  • the dendrimers according to the invention can be prepared according to methods known to the person skilled in the art or in analogy thereto. Suitable methods are described in the literature, such as. In Frechet, Jean MJ; Hawker, Craig J.,
  • hyperbranched polyesters new soluble, three-dimensional, reactive polymers ", Reactive & Functional Polymers (1,995), 26 (1-3), 127-36;
  • formulations of the compounds according to the invention are required. These formulations may be, for example, solutions, dispersions or emulsions. It may be preferable to use mixtures of two or more solvents for this purpose. Suitable and preferred
  • Solvents are, for example, toluene, anisole, o, m- or p-xylene,
  • Methyl benzoate mesitylene, tetralin, veratrole, THF, methyl THF, THP, chlorobenzene, dioxane, phenoxytoluene, especially 3-phenoxytoluene, (-) - fenchone, 1, 2,3,5-tetramethylbenzene, 1, 2,4,5 Tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidinone, 3-methylanisole, 4-methylanisole, 3,4-dimethylanisole, 3,5-dimethylaniso !, acetophenone, ⁇ -terpineol, benzothiazole, butyl benzoate, cumene,
  • Tripropylene glycol dimethyl ether Tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-isopropylnaphthalene, pentylbenzene, hexylbenzene, heptylbenzene,
  • the invention therefore further provides a formulation, in particular a solution, dispersion or emulsion, comprising at least one compound of the formula (1) or (2), or at least one polymer, oligomer or dendrier containing at least one unit of the formula (1) , or (2), as well as at least one solvent, preferably an organic solvent.
  • a formulation in particular a solution, dispersion or emulsion, comprising at least one compound of the formula (1) or (2), or at least one polymer, oligomer or dendrier containing at least one unit of the formula (1) , or (2), as well as at least one solvent, preferably an organic solvent.
  • the compounds according to formula (1), or (2) are suitable for use in electronic devices, in particular in organic
  • Electroluminescent devices OLEDs
  • Electroluminescent device used. Preference is given to
  • Hole injection layer used as matrix materials in an emitting layer, as electron blocking materials, as exciton blocking materials, and / or as materials for an interlayer.
  • the electronic devices are preferably selected from the group consisting of organic integrated circuits (O-ICs), organic field-effect transistors (O-FETs), organic thin-film transistors (O-TFTs), organic light-emitting transistors (O-LETS), organic solar cells (O-SCs), organic optical Detectors, organic photoreceptors, organic field quench devices (O-FQDs),
  • O-ICs organic integrated circuits
  • O-FETs organic field-effect transistors
  • O-TFTs organic thin-film transistors
  • O-LETS organic light-emitting transistors
  • O-SCs organic solar cells
  • organic optical Detectors organic photoreceptors
  • O-FQDs organic field quench devices
  • Laser diodes and particularly preferably organic
  • Electroluminescent devices comprising the anode, cathode and at least one emitting layer, characterized in that at least one organic layer, which may be an emitting layer, a hole transport layer or another layer, comprises at least one compound according to formula (1), or (2) contains.
  • the organic electroluminescent device may contain further layers. These are, for example, selected from one or more
  • Electron blocking layers exciton blocking layers
  • the organic electroluminescent device may also include a plurality of emitting layers.
  • these emission layers particularly preferably have a total of a plurality of emission maxima between 380 nm and 750 nm, so that overall white emission results, ie in the emitting layers different emitting compounds are used which fluoresce or
  • Three-layer systems ie systems with three emitting layers, wherein at least one of these layers at least one compound according to formula (1), or (2) contains and wherein the three layers blue, green and orange or red emission show (for the basic structure see, for WO 2005/01 1013).
  • the compounds according to the invention may also be present in the hole transport layer and / or in an interlayer. It should be noted that, for the production of white light, instead of a plurality of color-emitting emitter compounds, a single-use emitter compound emitting in a wide wavelength range may also be suitable.
  • the compound according to formula (1) or (2) is used in an electronic device containing one or more phosphorescent dopants.
  • the compound according to formula (1) or (2) is used in an electronic device containing one or more phosphorescent dopants.
  • the compound in different layers, preferably in one
  • emitting layer can be used.
  • the compound according to formula (1) or (2) can also be used according to the invention in an electronic device containing one or more fluorescent dopants.
  • phosphorescent dopants are typically
  • Preferred phosphorescence emitters used are compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold or europium, in particular compounds containing iridium, platinum or copper.
  • Phosphorescent complexes as used in the prior art for phosphorescent OLEDs and how they
  • Phosphorescent dopants are removed.
  • Hole transport layer and / or used in a hole injection layer are used in a hole injection layer.
  • a hole injection layer in the sense of this invention is a layer which is directly adjacent to the anode.
  • a hole transport layer in the sense of this invention is a layer that lies between the hole injection layer and the emission layer. The hole transport layer can directly to the
  • Adjacent emission layer When the compounds according to formula (1), or (2) are used as hole transport material or as hole injection material, it may be preferable if they are with
  • Electron-acceptor compounds are doped, for example, with F4-TCNQ or with compounds, as described in EP 1476881 or EP 1596445.
  • Hexaazatriphenylene derivative as described in US 2007/0092755.
  • the Hexaazatriphenylenderivat is used in a separate layer.
  • the compound according to formula (1), or (2) is used as hole transport material in a hole transport layer
  • the compound can be used as a pure material, ie in a proportion of 100%, in the hole transport layer, or it can be used in combination with one or several other compounds are used in the hole transport layer.
  • the compounds of the formula (1) or (2) are used as matrix material in combination with one or more dopants, preferably phosphorescent dopants.
  • a dopant in a system comprising a matrix material and a dopant, is understood to mean the component whose proportion in the mixture is the smaller.
  • a matrix material in a system containing a matrix material and a dopant is understood to mean the component whose proportion in the mixture is the larger.
  • the proportion of the matrix material in the emitting layer in this case is between 50.0 and 99.9% by volume, preferably between 80.0 and 99.5% by volume and particularly preferred for fluorescent emitting layers between 92.0 and 99.5% by volume and for phosphorescent emitting layers between 85.0 and 97.0 vol.%.
  • the proportion of the dopant is between 0.1 and 50.0% by volume, preferably between 0.5 and 20.0% by volume and particularly preferred for fluorescent emitting layers between 0.5 and 8.0% by volume and for phosphorescent emitting layers between 3.0 and 15.0% by volume. -%.
  • Electroluminescent device may also contain systems comprising a plurality of matrix materials (mixed-matrix system) and / or multiple dopants. Also in this case the dopants are in general.
  • Matrix material in the system to be smaller than the share of a single
  • the mixed-matrix systems preferably comprise two or three different matrix materials, more preferably two different matrix materials.
  • different matrix materials can be present in a ratio of 1:10 to 1: 1, preferably in a ratio of 1: 4 to 1: 1.
  • the mixed-matrix systems may comprise one or more dopants.
  • the dopant compound or the dopant compounds together according to the invention have a proportion of 0.1 to 50.0% by volume of the total mixture and preferably a fraction of 0.5 to 20.0% by volume of the total mixture. Accordingly, the matrix components together have a proportion of 50.0 to 99.9% by volume of the total mixture and preferably a proportion of 80.0 to 99.5% by volume of the
  • Particularly suitable matrix materials which can be used in combination with the compounds according to the invention as matrix components of a mixed-matrix system are aromatic ketones, aromatic phosphine oxides or aromatic sulfoxides or sulfones, eg. B according to WO 04/013080, WO 04/093207, WO 06/005627 or WO
  • Carbazole derivatives indolocarbazole derivatives, e.g. B. according to WO 07/063754 or WO 08/056746, Azacarbazolderivate, z. B. according to EP 1617710, EP 1617711, EP1731584, JP 2005/347160, bipolar matrix materials, eg. B. according to WO 07/137725, silanes, z. B. according to WO 05/111172, azaborole or boronic esters, for. B. according to WO 06/117052, triazine derivatives, z. B. according to the application WO 2010/015306, WO 2007/063754 or
  • Preferred phosphorescent dopants for use in mixed-matrix systems comprising the compounds according to the invention are the phosphorescent compounds listed in a table below
  • Interlayer used Interlayers are preferably used in organic electroluminescent devices comprising a plurality of emitting layers, for example in white-emitting OLEDs which each contain a red-emitting, a green-emitting and a blue-emitting layer. Particularly preferably, intermediate layers are arranged between two emitting layers.
  • An intermediate layer comprising a compound according to the invention is, according to a preferred embodiment of the invention, between the blue-emitting layer and the green-emitting layer of a white-light-emitting OLED which has a red color
  • the blue-emitting layer is particularly preferably a fluorescent layer
  • the green-emitting layer is a phosphorescent layer.
  • Preferred fluorescent dopants are selected from the class of arylamines.
  • An arylamine or an aromatic amine in the sense of this invention is understood as meaning a compound which comprises three substituted or unsubstituted aromatic or heteroaromatic ring systems contains bound directly to the nitrogen. At least one of these aromatic or heteroaromatic ring systems is preferably one
  • fused ring system more preferably having at least 14 aromatic ring atoms.
  • Preferred examples thereof are aromatic anthraceneamines, aromatic anthracenediamines, aromatic
  • Aromatic pyrenamine Pyrenamines, aromatic pyrenediamines, aromatic chrysenamines or aromatic chrysendiamines.
  • aromatic anthracene amine is meant a compound in which a diarylamino group is bonded directly to an anthracene group, preferably in the 9-position.
  • An aromatic anthracenediamine is understood to mean a compound in which two diarylamino groups are bonded directly to an anthracene group, preferably in the 9,10-position.
  • Aromatic pyrenamine Aromatic pyrenamine
  • Pyrene diamines, chrysenamines and chrysenediamines are defined analogously thereto, the diarylamino groups on the pyrene preferably being bonded in the 1-position or in the 1, 6-position.
  • Further preferred fluorescent dopants are selected from indenofluorenamines or -diamines, for example according to WO 2006/122630, benzoindenofluorenamines or -diamines, for example according to WO 2008/006449, and
  • Dibenzoindenofluorenamines or diamines for example according to WO 2007/140847. Further preferred are those in WO 2010/012328
  • Suitable fluorescent dopants are furthermore those disclosed in JP 2006100 1973, WO 2004/047499, WO 2006/098080, WO 2007/065678, US Pat
  • Suitable matrix materials are materials of different substance classes. preferred
  • Matrix materials are selected from the classes of oligoarylenes (z. B. 2,2 ', 7,7, -Tetraphenylspirobifluoren according to EP 676461 or Dinaphthylanthracene), in particular containing the oligoarylenes
  • the condensed aromatic groups eg DPVBi or spiro-DPVBi according to EP 676461
  • the polypodal metal complexes eg according to WO 2004/081017
  • the hole-conducting compounds eg.
  • WO 2004/058911 the electron-conducting compounds, in particular ketones, phosphine oxides, sulfoxides, etc. (for example according to WO 2005/084081 and WO 2005/084082), the atropisomers (for example according to WO 2006/048268) , the boronic acid derivatives (for example according to WO 2006/117052) or the benzanthracenes (for example according to WO 2008/145239).
  • Particularly preferred matrix materials are selected from the classes of
  • Very particularly preferred matrix materials are selected from the classes of
  • Oligoarylenes containing anthracene, benzanthracene, benzphenanthrene and / or pyrene or atropisomers of these compounds are to be understood as meaning a compound in which at least three aryl or arylene groups are bonded to one another.
  • Preferred matrix materials for phosphorescent dopants are, in addition to the compounds according to the invention, carbazole derivatives (eg CBP ( ⁇ , ⁇ -biscarbazolylbiphenyl) or compounds according to WO 2005/039246, US 2005/0069729, JP 2004/288381, EP 1205527 or WO 2008/086851) , Triarylamines, azacarbazoles (for example according to EP 1617710, EP 1617711, EP 1731584, JP 2005/347160), indolocarbazole derivatives, e.g. For example, according to WO 2007/063754 or WO 2008/056746, ketones (for example according to WO
  • phosphine oxides for example according to WO 2005/003253
  • oligophenylenes for example according to US 2005/0069729
  • bipolar matrix materials eg. according to WO 2007/137725
  • silanes for example according to WO 2005/11 1172
  • azaboroles or boronic esters eg. B. according to WO 2006/117052
  • Triazine derivatives e.g. In accordance with WO 201 0/015306, WO 2007/063754 or WO 2008/056746, zinc complexes (for example according to WO 20091062578),
  • Aluminum complexes e.g., BAIq
  • diazasilol and tetraazasilol derivatives e.g. B. according to WO 2010/054730
  • indenocarbazole derivatives z. B. according to WO 2010/136109 and WO 201 1/000455 or diazaphosphole, z. B. according to WO 2010/054730.
  • Suitable charge transport materials as used in the hole injection or hole transport layer or in the electron transport layer of the
  • low work function metals, metal alloys or multilayer structures of various metals are preferable, such as alkaline earth metals, alkali metals, main group metals or lanthanides (eg, Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.).
  • alkaline earth metals alkali metals, main group metals or lanthanides (eg, Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.).
  • alloys of an alkali or alkaline earth metal and silver for example an alloy of magnesium and silver.
  • further metals which have a relatively high work function such as, for example, As Ag or Al, which then usually combinations of metals, such as Ca / Ag, Ba / Ag or Mg / Ag are used.
  • a metallic cathode and the organic semiconductor may also be preferred to introduce between a metallic cathode and the organic semiconductor a thin intermediate layer of a material with a high dielectric constant.
  • a metallic cathode and the organic semiconductor a thin intermediate layer of a material with a high dielectric constant.
  • Suitable examples of this are alkali metal or alkaline earth metal fluorides, but also the corresponding oxides or carbonates (eg LiF, Li 2 O, BaF 2, MgO, NaF, CsF, Cs 2 CO 3 , etc.).
  • lithium-quinolinate can be used for this purpose (LiQ) can be used.
  • the layer thickness of this layer is preferably between 0.5 and 5 nm.
  • the anode high workfunction materials are preferred.
  • the anode has a work function greater than 4.5 eV. Vacuum up.
  • metals with high redox potential are suitable, such as
  • Metal / metal oxide electrode (z. B. AI / Ni / NiO x> AI / PtO x) may be preferred.
  • at least one of the electrodes must be transparent or partially transparent to allow either the irradiation of the organic material (organic solar cell) or the outcoupling of light (OLED, O-LASER).
  • Preferred anode materials are conductive mixed metal oxides. Particularly preferred are indium tin oxide (ITO) or indium zinc oxide (IZO). Preference is furthermore given to conductive, doped organic materials, in particular conductive doped polymers.
  • the device is structured accordingly (depending on the application), contacted and finally sealed, since the life of the devices according to the invention is shortened in the presence of water and / or air.
  • Organic electroluminescent device characterized in that one or more layers are coated by a sublimation process.
  • the materials are vacuum deposited in vacuum sublimation at an initial pressure less than 10 "5 mbar, preferably less than 10 " 6 mbar. However, it is also possible that the initial pressure is even lower, for example, less than 10 "7 mbar.
  • an organic electroluminescent device characterized in that one or more layers with the OVPD (Organic Vapor Phase Deposition) process or coated by means of a carrier gas sublimation.
  • the materials are applied at a pressure between 10 "applied 5 mbar and 1 bar.
  • OVJP organic vapor jet printing
  • the materials are applied directly through a nozzle and patterned (eg. BMS Arnold et al., ⁇ . Phys. Lett. 2008, 92, 053301).
  • an organic electroluminescent device characterized in that one or more layers of solution, such. B. by spin coating, or with any printing process, such.
  • any printing process such as screen printing, flexographic printing, Nozzle Printing or offset printing, but particularly preferably LITI (Light Induced Thermal Imaging, thermal transfer printing) or ink-jet printing (ink jet printing), are produced.
  • LITI Light Induced Thermal Imaging, thermal transfer printing
  • ink-jet printing ink jet printing
  • organic electroluminescent devices comprising one or more compounds according to the invention can be used in displays as
  • Light sources in lighting applications and as light sources in medical and / or cosmetic applications are used.
  • the compounds according to the invention are distinguished in particular by the fact that when used in organic
  • Electroluminescent devices good power efficiencies, low
  • the compounds are resistant to oxidation, stable in temperature and have a high glass transition temperature, which is advantageous both for processability, for example from solution or from the gas phase, as well as for use in electronic devices.
  • the compounds have a high hole mobility, which in particular when used as a hole transport material or
  • Hole injection material is highly desirable.
  • the starting materials can be obtained from the companies ALDRICH or ABCR (palladium (II) acetate, tri-o-tolylphosphine, inorganics, solvents).
  • Residue is suspended in the heat at 40 ° C in 500 ml of glacial acetic acid, the suspension is treated with 0.5 ml of conc. Sulfuric acid is added, and
  • inventive OLEDs and OLEDs according to the prior art is carried out according to a general method according to WO 04/05891 1, based on the conditions described here
  • Reference examples V1 and V2 introduce the data of different OLEDs.
  • the substrates used are glass plates coated with structured ITO (indium tin oxide) of thickness 50 nm.
  • the OLEDs have in principle the following layer structure: Substrate / p-doped hole transport layer A '(HIL1) / hole transport layer A (HTL) / p-doped hole transport layer B (HIL2) / hole transport layer C (EBL) /
  • Emission Layer Emission Layer
  • ETL Electron Transport Layer
  • Electron injection layer EIL
  • cathode is formed by a 100 nm thick aluminum layer.
  • Table 1 The materials needed to make the OLEDs are shown in Table 1, the construction of the various manufactured electronic devices in Table 2. All materials are thermally evaporated in a vacuum chamber.
  • the emission layer always consists of at least one
  • Matrix material (host material, host material) and an emitting dopant (dopant, emitter), the matrix material or the
  • H1 SEB (5%) here means that the material H1 is present in a proportion by volume of 95% and SEB in a proportion of 5% in the layer. Analog can also the
  • Electron transport layer or hole injection layers consist of a mixture of two materials.
  • the OLEDs are characterized by default. For this, the electroluminescence spectra, the current efficiency (measured in cd / A), the power efficiency (measured in Im / W) and the external quantum efficiency (EQE, measured in percent) as a function of the luminance, calculated from current-voltage-luminance characteristics ( IUL characteristics) assuming a Lambertian radiation characteristic and the
  • the electroluminescence spectra are determined at a luminance of 1000 cd / m 2 and from this the CIE 1931 x and y color coordinates are calculated.
  • the term EQE @ 10 mA cm 2 denotes the external quantum efficiency at a current density of 10 mA / cm 2 .
  • LD80 @ 60 mA / cm2 is the lifetime up to which the starting brightness of the considered OLED has dropped from 60 mA / cm 2 to 80% of the initial intensity at a constant current.
  • a blue fluorescent reference sample V1 was prepared and compared with the inventive samples E1 to E7.
  • the reference sample V1 has an external quantum efficiency of 6.2% and a lifetime (LD80 @ 60 mA / cm 2 ) of 120 h at a current density of 10 mA / cm 2 .
  • the samples according to the invention have E1 (7.5%, 160 h), E2 (7.8%, 250 h), E3 (7.6%, 210 h), E4 (7.4%, 200 h), E5 (8.0%, 235 h) , E6 (7.7%, 270 h) and E7 (7.1%, 260 h) both better external
  • Quantum efficiency at a current density of 10 mA / cm 2 as well as longer life (LD80 @ 60 mA / cm 2 ).
  • a green reference phosphorescent sample V2 was prepared and compared with the inventive samples E8 to E12. The
  • Reference sample V2 has an external quantum efficiency of 11.7% and a lifetime (LD80 @ 20 mA / cm 2 ) of 80 h at a current density of 2 mA / cm 2 .
  • the samples according to the invention have E8 (17.2%, 135 h), E9 (18.7%, 110 h), E10 (17.4%, 145 h), E11 (19.0%, 105 h) and E12 (20.2%, 160 h ) both better external quantum efficiency at a current density of 2 mA / cm 2 , as well as longer life (LD80 @ 20 mA / cm 2 ).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electroluminescent Light Sources (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
PCT/EP2014/002586 2013-10-23 2014-09-24 Materialien für elektronische vorrichtungen WO2015058826A1 (de)

Priority Applications (6)

Application Number Priority Date Filing Date Title
EP14772289.6A EP3060623B1 (de) 2013-10-23 2014-09-24 Materialien für elektronische vorrichtungen
CN201480057646.1A CN105722944A (zh) 2013-10-23 2014-09-24 用于电子器件的材料
US15/030,565 US9859502B2 (en) 2013-10-23 2014-09-24 Materials for electronic devices
KR1020167013361A KR102279289B1 (ko) 2013-10-23 2014-09-24 전자 소자용 물질
JP2016525945A JP6469673B2 (ja) 2013-10-23 2014-09-24 電子素子のための材料
KR1020217021857A KR20210091355A (ko) 2013-10-23 2014-09-24 전자 소자용 물질

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP13005070 2013-10-23
EP13005070.1 2013-10-23

Publications (1)

Publication Number Publication Date
WO2015058826A1 true WO2015058826A1 (de) 2015-04-30

Family

ID=49553974

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2014/002586 WO2015058826A1 (de) 2013-10-23 2014-09-24 Materialien für elektronische vorrichtungen

Country Status (6)

Country Link
US (1) US9859502B2 (ko)
EP (1) EP3060623B1 (ko)
JP (1) JP6469673B2 (ko)
KR (2) KR102279289B1 (ko)
CN (2) CN112047845A (ko)
WO (1) WO2015058826A1 (ko)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016113396A (ja) * 2014-12-15 2016-06-23 三星ディスプレイ株式會社Ｓａｍｓｕｎｇ Ｄｉｓｐｌａｙ Ｃｏ．，Ｌｔｄ． アミン化合物、および有機電界発光素子
KR20170088650A (ko) * 2016-01-25 2017-08-02 주식회사 엘지화학 화합물 및 이를 포함하는 유기 전자 소자
US11563179B2 (en) 2014-05-13 2023-01-24 Samsung Sdi Co., Ltd. Compound, organic optoelectronic element comprising same and display device thereof

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016158191A1 (ja) * 2015-03-30 2016-10-06 新日鉄住金化学株式会社 有機電界発光素子
KR101865051B1 (ko) * 2016-07-15 2018-06-08 주식회사 알파켐 신규한 유기발광화합물 및 이를 포함하는 유기 발광 소자
TW201831468A (zh) * 2016-12-05 2018-09-01 德商麥克專利有限公司 含氮的雜環化合物
TWI791481B (zh) * 2017-01-30 2023-02-11 德商麥克專利有限公司 形成有機電致發光（ｅｌ）元件之方法
KR101857632B1 (ko) 2018-02-02 2018-05-14 덕산네오룩스 주식회사 유기전기소자용 화합물, 이를 이용한 유기전기소자 및 그 전자 장치
CN112062718B (zh) * 2019-05-25 2024-02-06 吉林奥来德光电材料股份有限公司 有机电致发光化合物和包含所述化合物的有机电致发光装置
KR20210038736A (ko) 2019-09-27 2021-04-08 삼성디스플레이 주식회사 축합환 화합물 및 이를 포함한 유기 발광 소자
KR20220048180A (ko) * 2020-10-12 2022-04-19 주식회사 엘지화학 신규한 화합물 및 이를 포함한 유기 발광 소자
CN116730799B (zh) * 2023-05-26 2024-01-12 西安欧得光电材料有限公司 一种含螺芴结构的oled化合物及其制备方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102030701A (zh) * 2010-11-04 2011-04-27 华东师范大学 一类Fluoradene衍生物及其制备方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006100896A1 (ja) * 2005-03-18 2006-09-28 Idemitsu Kosan Co., Ltd. 芳香族アミン誘導体及びそれを用いた有機エレクトロルミネッセンス素子

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102030701A (zh) * 2010-11-04 2011-04-27 华东师范大学 一类Fluoradene衍生物及其制备方法

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
AIBING XIA ET AL: "Two fluoradene derivatives: pseudosymmetry, eccentric ellipsoids and a phase transition Two fluoradene derivatives: pseudosymmetry, eccentric ellipsoids and a phase transition", ACTA CRYSTALLOGRAPHICA SECTION B, STRUCTURAL SCIENCE, vol. B57, 1 January 2001 (2001-01-01), pages 507 - 516, XP055153468 *
CHRISTIAN TUCHSCHERER ET AL: "Preparation of 2H-cyclopenta[j,k]fluorene and substituted fluoradenes", TETRAHEDRON LETTERS, vol. 11, 1 January 1973 (1973-01-01), pages 865 - 868, XP055153488 *
LINGLING RONG ET AL: "Fluoradenes via palladium-catalyzed intramolecular arylation", CHEMICAL COMMUNICATIONS, vol. 47, no. 7, 1 January 2011 (2011-01-01), pages 2155, XP055153455, ISSN: 1359-7345, DOI: 10.1039/c0cc05004k *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11563179B2 (en) 2014-05-13 2023-01-24 Samsung Sdi Co., Ltd. Compound, organic optoelectronic element comprising same and display device thereof
JP2016113396A (ja) * 2014-12-15 2016-06-23 三星ディスプレイ株式會社Ｓａｍｓｕｎｇ Ｄｉｓｐｌａｙ Ｃｏ．，Ｌｔｄ． アミン化合物、および有機電界発光素子
KR20170088650A (ko) * 2016-01-25 2017-08-02 주식회사 엘지화학 화합물 및 이를 포함하는 유기 전자 소자
KR101896151B1 (ko) * 2016-01-25 2018-09-07 주식회사 엘지화학 화합물 및 이를 포함하는 유기 전자 소자

Also Published As

Publication number Publication date
JP6469673B2 (ja) 2019-02-13
EP3060623A1 (de) 2016-08-31
US20160268509A1 (en) 2016-09-15
CN112047845A (zh) 2020-12-08
EP3060623B1 (de) 2018-11-07
US9859502B2 (en) 2018-01-02
JP2016535735A (ja) 2016-11-17
CN105722944A (zh) 2016-06-29
KR20210091355A (ko) 2021-07-21
KR102279289B1 (ko) 2021-07-19
KR20160074630A (ko) 2016-06-28

Similar Documents

Publication Publication Date Title
EP3080229B1 (de) Materialien für elektronische vorrichtungen
EP3057947B1 (de) Materialien für elektronische vorrichtungen
EP2705552B1 (de) Verbindungen für elektronische vorrichtungen
EP2931698B1 (de) Materialien für elektronische vorrichtungen
EP3060623B1 (de) Materialien für elektronische vorrichtungen
WO2017036574A1 (de) 6,9,15,18-tetrahydro-s-indaceno[1,2-b:5,6-b']difluoren- derivate und ihre verwendung in elektronischen vorrichtungen
WO2017025165A1 (de) Materialien für elektronische vorrichtungen
EP3016952B1 (de) Spirokondensierte lactamverbindungen für organische elektrolumineszenzvorrichtungen
WO2012149999A1 (de) Verbindungen für elektronische vorrichtungen
EP2941472A1 (de) Materialien für elektronische vorrichtungen
WO2012048780A1 (de) Verbindungen für elektronische vorrichtungen
WO2013087142A1 (de) Verbindungen für elektronische vorrichtungen
EP2875699A1 (de) Derivate von 2-diarylaminofluoren und diese enthaltnde organische elektronische verbindungen
WO2014037077A1 (de) Verbindungen für elektronische vorrichtungen
WO2014079527A1 (de) Materialien für elektronische vorrichtungen
WO2013017189A1 (de) Verbindungen für elektronische vorrichtungen
EP3335254A1 (de) Materialien für organische elektrolumineszenzvorrichtungen
WO2011057701A1 (de) Organische verbindungen für elektroluminiszenz vorrichtungen
WO2015049022A1 (de) Triarylamin-substituierte benzo[h]chinolin-derivate als materialien für elektronische vorrichtungen
WO2014106524A2 (de) Materialien für elektronische vorrichtungen
WO2011157346A1 (de) Verbindungen für elektronische vorrichtungen
WO2016045765A1 (de) Materialien für organische elektrolumineszenzvorrichtungen
EP2984150A1 (de) Materialien für elektronische vorrichtungen
WO2019048458A1 (de) Materialien für elektronische vorrichtungen

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14772289

Country of ref document: EP

Kind code of ref document: A1

REEP Request for entry into the european phase

Ref document number: 2014772289

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2014772289

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 15030565

Country of ref document: US

ENP Entry into the national phase

Ref document number: 2016525945

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 20167013361

Country of ref document: KR

Kind code of ref document: A